Bis-maleamic compounds

ABSTRACT

D R A W I N G

ilniied Statics Patent [72] Inventors Lucien Bonnard;

Pierre Grosjean, both of Lyon, France [21 Appl. No. 707,283 [22] FiledFeb. 21, 1968 [45] Patented Dec. 14, 1971 [73] Assignee SocieteRhodiaceta Paris, France [32] Priority Feb. 28, 1967 [33] France [3196,872

[54] BlS-MALEAMIC COMPOUNDS 7 Claims, No Drawings [52] US. Cl 260/326.3,260/41 A, 260/78 UA [51] Int. Cl C07d 27/18 [50] Field of Search260/326.3

[56] References Cited UNITED STATES PATENTS 2,643,258 6/1953 Miller eta]. 260/326.5 2,980,694 4/1961 Sauers et al. 260/32615 2,989,504 6 lQ6 ll itile.... 7 260/62 3,337,584 8/1967 Knock 3,431,276 3/1969 NieldPrimary ExaminerNicholas S. Rizzo Assistant Examiner-Joseph A. NarcavageAttorney-Cushman, Darby & Cushman ABSTRACT: New bis-imides of formula: I1

group and R" is hydrogen or lower alkyl, and made by dehydrating newacids of formula:

II I! in which R, R and R are as above. The bis-imides can be formedinto moulded cross-linked polymers by heating.

BlS-MALEAMIC COMPOUNDS This invention relates to new bis-maleamiccompounds, and to the imides and polymides made therefrom. These newcompounds have the formula in which R is a hydrogen atom or alkyl,cycloalkyl or aryl radical, R is an alkyl, cycloalkyl or aryl radical,or R and R together form an alkylene radical, and R" is a hydrogen atomor a lower alkyl radical (i.e. an alkyl radical containing one to fourcarbon atoms).

These compounds are yellow solids of high melting point.

X being a divalent radical of formula.

R, R' and Rf havingthe meanings already given.

The diamines which may be employed include diaminodiphenylalkanes suchas 2,2-bis(p-aminophenyl)propane, l-bis(aminophenyl)cycloalkanes such as1,1- bis(p-aminophenyl)cyclohexane, and diaminotriphenylalkanes such asl l -bis( p aminophenyl)- l-phenylethane.

The condensation can be carried out in a solvent medium preferablyconsisting of a mixture of dimethylfonnamide and acetone at atemperature below C. The bis-maleamic compounds are obtained in the formof precipitates.

On heating these compounds to a temperature between 40 and 60 C. withacetic anhydride in the present of sodium acetate, preferably in aliquid medium such as dimethylformamide they are dehydrated to thecorresponding bis-imides in accordance with the reaction;

New three-dimensional (cross-linked) polyimides are obtained in the formof powder or of shaped objects by heating the aforesaid bis-imides at atemperature between 80 and 400 C. The bis-imides may be mixed withfillers, which will then become incorporated in the polymers.

The bis-maleamic compounds and the bis-imides of the invention may alsobe employed for cross-linking polymers such as polyethylene andpolyoxymethylene.

The following example illustrate the invention.

EXAMPLE I 3.3 mol of maleic anhydride is dissolved in 350 cc. ofacetone, and the solution obtained is introduced into a 2-liter reactorprovided with a stirrer and a thermometer, and placed in a cooling bathconsisting of a mixture of water and ice.

1.5 mol of l,l-bis(p-aminophenyDcyclohexane in solution in 800 cc. of asolvent consisting of a mixture of dimethyl formamide and chloroform inequal volumes is slowly introduced into the reactor with vigorousstirring. The rate of flow is so adjusted that the temperature of thereaction mass remains below 20 C.

The bis-maleamic compound precipitates as it is formed and is recoveredby filtration at the end of the reaction.

After washing with acetone and drying at 40 C. in vacuo, there isobtained 620 g. of a product of the formula:

It has a melting point of 280 C.

EXAMPLES 2, 3, 4, 5 and 6 By the procedure of example I, the productsshown in the following table are prepared from the diamines indicated:

7 EXAMPLE 7 Into a l-liter glass reactor provides with a thermometer anda central stirring system and heated by a water bath are introduced:

0.5 mol of the compound obtained in example I 1.5 mol of aceticanhydride 300 cc. of dimethyl formamide 10 g. of sodium acetate Thetemperature'is gently raised to 60 C., and the reaction mass ismaintained at this temperature for 1 hour. After cooling to l5 C., theexcess of anhydride is destroyed by adding a little water, and thebis-imide of the formula; v

CO-GH CH- C O\ CHC C O--CH crystallizes out.

Afier filtration, 170 g. of the bis-imide is obtained, which afterwashing with water and drying in vacuo at 40 C. has a melting point of 21 3 C.

EXAMPLES 8,9, l0, l1 and 12 By the procedure of example 7, the followingbis-imides are and 6.

EXAMPLEJ} Ten grams of l,l-bis(p-maleimidophenyl)cyclohexane prepared inexample 7 is heated until it has completely melted. Six grams ofpowdered silica isadded, and when this mixture has been degasified it ispoured into a mould and heated at 200 C. for 3 days. An infusible andinsoluble moulded article is obtained.

We claim:

A compound ofthgfgrmulag N 7 R II 3 If /CO-CH H Wm R C O- H in which R"is hydrogen or lower alkyl, and R and R together are pentamethylene or Ris lower alkyl or phenyl and R is lower alkyl or phenyl, or hydrogenwhen R'is phenyl.

H--CO prepared from the compounds obtained in examples 2 3, 4,

v g A bis-imide of the formula:

CH-C (l()-(lll 3. A bis-imide of the formula:

10 CHC0\ CH: 0 o en is A H 4. A bis-imide of the formula:

7 5. A bis-imide of the formula:

0H. CH; CH-C 00-011

2. A bis-imide of the formula:
 3. A bis-imide of the formula:
 4. Abis-imide of the formula:
 5. A bis-imide of the formula:
 6. A bis-imideof the formula:
 7. A bis-imide of the formula: